JPS63179916A - Thermoplastic polyurethane resin for moisture-permeable and waterproofing material - Google Patents

Abstract

PURPOSE:To obtain the titled resin, containing polysiloxanediol and polyoxytetramethylene glycol, etc., in a specific proportion as soft segment and capable of providing films having excellent surface slipperiness, light fastness, hydrolytic resistance, etc., and improved moisture permeability as well as water repellency. CONSTITUTION:A polyurethane resin, constituted of soft segments consisting of (A) a polysiloxanediol having 600-3,000 average molecular weight, (B) polyoxytetramethlylene glycol having 800-2,200 average molecular weight and, if necessary, (C) other diols and hard segments consisting of (D) an aliphatic diisocyanate and (E) an aliphatic diamine and containing 3-50wt.% component (A) and the component (B) in an amount of 0.6 based on the component (A). For example, the above-mentioned resin is obtained by initially carrying out reaction at 1/1.3-1/4.5 ratio of OH groups of the soft segment to NCO groups of the a component (D) to prepare a prepolymer and then extending the chain with the component (E).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a new and useful thermoplastic polyurethane resin for moisture permeable and waterproof materials having excellent moisture permeability and waterproof properties. This invention relates to a thermoplastic polyurethane resin that is composed of a soft segment and a hard segment and is suitable for moisture-permeable and waterproof materials for use in clothing, various industrial materials, medical materials, etc.

[Conventional technology]

By the way, base materials for clothing are required to have many physical properties such as moisture permeability, light resistance, NOx resistance (oxidant resistance), surface smoothness, water repellency, flexibility, hydrolysis resistance, and washing resistance. It is well known that Among these, as sports clothing becomes more popular, it has become essential to have both high moisture permeability and excellent waterproofness.

Conventionally, in order to obtain a highly moisture-permeable film, whether it is a polyurethane film or other synthetic resin film, there are two methods: to make the film porous, or to make the resin hydrophilic without making it porous. It depends on the method.

[Problem that the invention seeks to solve]

However, although high moisture permeability can be obtained by making the film porous, on the other hand,
This processing method itself is relatively complicated, and furthermore, it is difficult to improve the strength of the resulting film, and water leakage is likely to occur.
Furthermore, there is a drawback that water resistance decreases during washing.

On the other hand, when using a method of making the resin hydrophilic, the processing method itself does not require much effort and a film with strong film strength can be obtained, but on the other hand, it is difficult to obtain high moisture permeability, and the resin may become The disadvantage is that by making the film hydrophilic, the water resistance and hydrolysis resistance of the film itself tend to deteriorate.

In this way, as long as the conventional method is followed,
It is no longer possible to obtain a highly moisture permeable film that is necessarily satisfactory.

[Means for solving problems]

However, the present inventors have found that the processing method itself is simple, the material is non-porous with no risk of water leakage, has high moisture permeability, is highly water repellent, has surface smoothness, light resistance, As a result of extensive research in order to provide a urethane resin with a good balance of NOx resistance, water resistance, and hydrolysis resistance, we found that the presence of a specific soft segment called polysiloxane diol met the above objectives. After discovering something, we have completed the present invention.

That is, in the present invention, the soft segment is 3 to 50% by weight based on the solid content of the thermoplastic polyurethane resin.
A polysiloxane diol with an average molecular weight of 600 to 3,000 and a content of 6 times or more of the polysiloxane diol and an average molecular weight of 800 to 2.00.
-0 polyoxynato 2 methylene glycol and, if necessary, other diols other than these polysiloxane diols and polyoxytetramethylene glycol; The object of the present invention is to provide a thermoplastic polyurethane resin for use in moisture permeable and waterproof materials, which is composed of diamine and has high moisture permeability and waterproof properties.

Here, the above-mentioned polysiloxane diol is
It is similar to the compound shown in .

The polyurethane of the present invention made of the polysiloxane diol is suitable. If the amount is less than 3% by weight, it becomes difficult to obtain sufficient water resistance and surface smoothness, and if it exceeds 50% by weight, the cost increases, which is not preferable.

Further, the average molecular weight of the polysiloxane diol is 60
If it is less than 0, the water repellency and lubricity peculiar to silicone cannot be maintained, and conversely, if it exceeds 3.0 [10, other urethane resin raw materials, such as polyoxytetramethylene glycol, etc. Since the compatibility with diols other than the polysiloxane diol and polyoxytetramethylene glycol, aliphatic diincyanate, and aliphatic diamine decreases, it becomes difficult to obtain a stable polyurethane resin solution, and as a result, the film becomes less uniform. Both are undesirable because they result in something missing.

The content of the polyoxytetramethylene glycol in the polyurethane resin of the present invention is 1], 6 times or more, preferably 0.6 to 5 times or more, the content of the polysiloxane diol as mentioned above. is necessary.

If the content of the polyoxytetramethylene glycol is less than 0.6 times the content of the above-mentioned polysiloxane diol, the compatibility with the polysiloxane diol will be significantly reduced, resulting in a uniform It becomes difficult to obtain a polyurethane resin film.

The average molecular weight of the polyoxytetramethylene glycol is suitably within the range of 800 to 2,200. Both when it is less than 800 and conversely when it exceeds 2,200, the compatibility with the above-mentioned polysiloxane diol decreases significantly, and therefore it becomes difficult to obtain a stable resin solution. Neither of these are good conditions.

On the other hand, the aforementioned aliphatic diisocyanate refers to compounds having two isocyanate groups in the molecule, and broadly includes compounds in which each isocyanate group is not directly bonded to an aromatic ring. Among these, representative compounds include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,
Examples include 4'-diisocyanate (hydrogenated MDI), hexamethylene diinocyanate (HDI), and hydrogenated xylylene diisocyanate (HXDI). These may be used alone or in combination of two or more.

Further, the aliphatic diamine refers to compounds having two amine groups in the molecule, and broadly includes compounds in which each amino group is not directly bonded to an aromatic ring. Among them, representative ones include dicyclohexylmethane-4,4'-diamine (hydrogenated MDA), ethylenediamine, and inphoronediamine (I
PDA) or hexamethylene diamine.

Furthermore, diols other than the above-mentioned polysiloxane diol and polyoxytetramethylene glycol used in preparing the thermoplastic polyurethane resin of the present invention may be diols generally used in the production of polyurethane resins. Any of them may be used, but typical examples include polyoxyalkylene-butanediol such as polyoxyethylene glycol or polyoxypropylene glycol;
1,4-butanediol, 1,5-bentanediol,
1,6-hexanediol, neopentyl glycol,
Compounds with two alcoholic hydroxyl groups in the molecule, such as 3-methyl-1,5-penmendiol/I/i-ol: These various glycols (diols), succinic acid, adipic acid, azelaic acid or ester diols with dibasic acids such as sepatic acid, phthalic acid, isophthalic acid or terephthalic acid, or carbonic acid; and diols obtained by complete ring-opening polymerization of γ-caprolactone.

In preparing the thermoplastic polyurethane resin of the present invention using the various urethane resin raw materials listed above, the preparation method is not limited, but long chain diols as soft segments can be used. The appropriate ratio of the hydroxyl group of the diisocyanate to the incyanate group of the aliphatic diisocyanate is about 1/1.3 to 1/4.5. It is recommended to follow the so-called prepolymer method, in which a prepolymer is chain-extended with an aliphatic diamine.

These series of reactions are generally carried out in a solution, and in doing so, the compatibility with various diols (glycols) including the polysiloxane diol in the urethane resin raw materials mentioned above, and the resulting In terms of compatibility with the thermoplastic polyurethane resin, dimethylformamide is used alone or in a mixed state with other solvents, or a mixed solvent of toluene and alcohols such as isopropanol, or toluene is used. It is preferable to use a mixed solvent of glycol ether and glycol ether such as ethyl cellosolve in any proportion.

Furthermore, if necessary, there is no problem in using a known and commonly used reaction catalyst in the thermoplastic polyurethane resin of the present invention, and furthermore, as long as the purpose and effect of the present invention are not impaired, known and commonly used pigments and fillers may be used. There is no problem in adding various additives such as light stabilizers or antioxidants.

〔Effect of the invention〕

Since the thus obtained thermoplastic polyurethane resin for moisture-permeable waterproof materials of the present invention contains polysilxane bonds in its molecules, the film obtained from the polyurethane pattern resin of the present invention not only has good surface smoothness. It has excellent water-selective repellency and high moisture permeability, as well as light resistance.
Because it has good NOx resistance, hydrolysis resistance, and washing resistance, it is ideal as a material for waterproofing and moisture permeability.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, parts and percentages are all based on weight unless otherwise specified.

The various physical properties of the obtained resin were evaluated in the following manner.

First, the strength and elongation, which consists of 100% modulus, breaking strength, and elongation at break, has a width of 5 and a distance between gauge lines of 20.
A strip-shaped film named wn was used as a sample, and the sample was heated to 20°C.
After aging for 3 days in a room with 65% R, H, the tensile speed was 600WI+II/m1 in the same room.
Measured under the conditions of n.

Next, moisture permeability was measured in accordance with JIS Z-0208 using a circular film with a radius of 30 m as a sample, at 40° C. and in an atmosphere of 90% ROH.

In addition, the surface smoothness was measured by preparing a film with a thickness of 20 μm on a glass substrate and using this sample as a sample at 20°C.
After aging for 6 days in a room with 65% R, H, the friction coefficient was measured and evaluated using rHEIDON-14J (a surface quality measuring machine manufactured by Heyton, West Germany) at a load of 20.9. .

Furthermore, water resistance was determined by dropping water droplets on the film and measuring the contact angle of the water droplets with a goniometer.
After immersing a film of the following size in water for 10 minutes, the areal swelling rate was determined and evaluated using the contact angle and water expansion gear, respectively.

Furthermore, the hydrolysis resistance of the film was 95% at 70°C.
After being kept in an R, H atmosphere for 4 days, the strength and elongation of the film was measured as described above, and the breaking strength retention rate was calculated from the strength and elongation values. .

In addition, the light resistance is determined by "Shimadzu Fade Tester 0F-20".
Using SJ [■ Fade meter manufactured by Takasugi Seisakusho],
Light irradiation was carried out for 100 hours at 66°C in an atmosphere of 40% H0, and then aged for 6 days in a room maintained at 20°C and 65% R, H, after which strength and elongation and yellowing were determined. (ΔN) was measured and evaluated.

Furthermore, NOx resistance is JIS L-0855 (old method)
NOx gas (oxidant gas) at twice the concentration according to
The film was exposed to light for 6 hours and then dried over a day and night, and then the degree of yellowing (ΔN) was measured and evaluated.

Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, an average molecular weight of 2. 45 parts of polysiloxane diol (using Shin-Etsu Silicone product), ODD, with an average molecular weight of 2. 45 parts of polyoxytetramethylene glycol (PTMG) having an average molecular weight of 2,000, 60 parts of poly(1,4-butanediol adipate) (PB) having an average molecular weight of 2,000, and 50 parts of toluene were charged. After dissolving, 50 parts of IPDI and 0.05 part of diptyltin dilaurate as a reaction catalyst were added to make 80
℃ for 4 hours, then 80 parts of toluene was added and cooled to below 50℃ until the incyanate equivalent was 110.
A solution of incyanate prepolymer 0 was obtained.

Separately, in a reaction vessel equipped with a stirrer, reflux condenser and thermometer, 25 parts of H, MDA, 190 parts of toluene,
300 parts of isopropanol (IPA), 14 parts and 0 parts of methylceronelube, and 0.15 parts of di-n-butylamine (D-nBA) as a reaction terminator were charged, and incyanate precipitate was added thereto. 270 of polymer solution
of the non-volatile components (N, N,
A colorless and transparent polyurethane resin solution having V, ) of 20% and a viscosity at 25° C. (the same applies hereafter) of 14,000 cps was obtained.

Example 2 As starting materials, 18 parts of polysiloxane diol with an average molecular weight of 2,000, 90 parts of PTMG with an average molecular weight of 2,000, and polysiloxane diol with an average molecular weight of 2,000 are used. J
(1,3-propylene glycol) (PPG) 42
A solution of inocyanate prepolymer having isocyanate equivalents of i and ioo was obtained in the same manner as in Example 1, except that 50 parts of inocyanate and toluene were used to dissolve them.

Thereafter, N, V
A colorless and transparent polyurethane resin solution having a viscosity of 20% and a viscosity of 9,600 cps was obtained.

Example 3 As starting materials, 90 parts of polysiloxane diol with an average molecular weight of 2,000, 60 parts of PTMG with an average molecular weight of 2,000, and 50 parts of toluene were used as starting materials, except that these were changed to dissolve them. In the same manner as in Example 1, a solution of an incyanate prepolymer having an incyanate equivalent of tloo was obtained.

Thereafter, N, N,
A colorless and transparent polyurethane resin solution having a V of 20% and a viscosity of 13,500 cps was obtained.

Example 4 As starting materials, 45 parts of polysiloxane diol with an average molecular weight of 2,000, 45 parts of PTMG with an average molecular weight of 2,000, 45 parts of polyethylene glycol (PEG) with an average molecular weight of 2,000, and toluene. The isocyanate equivalent was 110 in the same manner as in Example 1, except that 50 parts of
A solution of isocyanate prepolymer 0 was obtained.

Thereafter, N, N,
A polyurethane resin solution having a V of 20% and a viscosity of 2100 cps was obtained.

Example 5 As starting materials, 45 parts of polysiloxane diol with an average molecular weight of too much, P with an average molecular weight of 1000
The solution was changed to 60 parts of TMG, 45 parts of PEG with an average molecular weight of 2,000, and 55 parts of toluene, and then the amount of IPDI to be added to this was changed to 60 parts, and the amount of toluene to be added was changed. Total amount used: 8
A solution of an isocyanate prepolymer having an incyanate equivalent of 1225 was obtained in the same manner as in Example 1, except that the amount was changed to 5 parts.

Thereafter, the amounts of H, MDA, ) toluene, IPA, methyl cellosolve and ])-nBA were adjusted to 20 parts each,
Example 1 except that the amounts were changed to 130 parts, 225 parts, 110 parts, and 0.12 parts, and the amount of side stones to be added to the incyanate prepolymer solution was also changed to 242 parts.
Similarly, N, V.

A colorless and transparent polyurethane resin solution having a viscosity of 20% and a viscosity of 15,000 cps was obtained.

Comparative Example 1 PTMG with an average molecular weight of 2,000 as a starting material
105 parts of PBA with an average molecular weight of 2,000
Example 1 was prepared in the same manner as in Example 1, except that 50 parts of isocyanate equivalents and toluene were used to dissolve them. An incyanate prepolymer solution called IDo was obtained.

Thereafter, a control polyurethane resin solution was obtained in the same manner as in Example 1, except that this control incyanate prepolymer solution was used. This thing is N
, V.

It was a colorless and transparent solution with a viscosity of 20% and a viscosity of 12,100 cps.

Comparative Example 2 PTMG with an average molecular weight of 2,000 as a starting material
Example 1 except that 60 parts of PEG with an average molecular weight of 2,000, 45 parts of PBA with an average molecular weight of 2,000, and 50 parts of toluene were used to dissolve these. Similarly, a control isocyanate prepolymer solution having an isocyanate equivalent of tloo was obtained.

Thereafter, a control polyurethane resin solution was obtained in the same manner as in Example 1, except that this control incyanate prepoly solution was used. This one is N.
It was a colorless and transparent solution with a V of 20% and a viscosity of 12,700 cps.

Comparative Example 3 As starting materials, 45 parts of polysiloxane diol with an average molecular weight of 2,000, 18 parts of PTMG with an average molecular weight of 2,000, and PB with an average molecular weight of 2,000.
A control inocyanate prepolymer solution having an isocyanate equivalent of tloo was obtained in the same manner as in Example 1, except that 87 parts of A and 50 parts of toluene were used to dissolve them.

Thereafter, a control polyurethane resin solution was obtained in the same manner as in Example 1, except that this control isocyanate prepolymer solution was used. This one is N,
It was a slightly cloudy solution with a V of 20% and a viscosity of 1,500 cps.

Moreover, the film obtained from this resin solution by a conventional method also became cloudy, and on the other hand, the resin solution itself separated after 3 days.

The physical properties of the films of the respective resins obtained in the above Examples and Comparative Examples were compared and examined. The results are summarized in Table 1.

As shown in Examples 1 to 5, the thermoplastic polyurethane resin of the present invention is tough, has excellent moisture permeability, and is hydrophobic with a contact angle with water exceeding 90 degrees. can be known.

For example, when hydrophilic PEG is copolymerized as in Examples 4 and 5, the water vapor permeability is further improved, and the contact angle greatly exceeds 90 degrees without getting wet with water, and it is still hydrophobic. It is worth noting that it holds.

In addition, the thermoplastic polyurethane resin of the present invention has surface smoothness,
It is no secret that it has excellent hydrolysis resistance, weather resistance, and NOx resistance.

On the other hand, as shown in Comparative Example 1, polyurethane resins that do not contain any polysiloxane diol have poor moisture permeability, poor surface smoothness, and are also poor in hydrolysis resistance and weather resistance. On the other hand, as shown in Comparative Example 2, when no polysiloxane diol is used at all, but when hydrophilic PEG is copolymerized, the moisture permeability improves. It is known that due to such hydrophilization, the hydrophobicity due to water swelling rate, contact angle, etc. further decreases, and the hydrolysis resistance is also extremely poor.

Furthermore, as shown in Comparative Example 3, a polyurethane resin in which the content of PTMG is less than α6 times the content of polysiloxane diol not only becomes cloudy by itself, but also has poor storage stability of the resin solution. I know it's bad.

Claims (1)

[Claims] The soft segment is 3 to 50% by weight based on the solid content of the thermoplastic polyurethane resin, and the average molecular weight is 600 to 600.
3,000 polysiloxane diol, polyoxytetramethylene glycol having an average molecular weight of 800 to 2,200, which is 0.6 times or more the content of this polysiloxane diol, and if necessary, the above-mentioned. A heat-permeable waterproof material comprising a polysiloxane diol and a diol other than polyoxytetramethylene glycol, and a hard segment comprising an aliphatic diisocyanate and an aliphatic diamine. Plastic polyurethane resin.